Improvements in or Relating to Organic Compounds

ABSTRACT

A stock solution comprising a compound of formula (I) 
     
       
         
         
             
             
         
       
         
         
           
             Wherein 
             R 1  together with the carbonyl group to which it is attached is a residue of a carboxylic acid, and NR 2 R 3 , in which R 3  is H or together with R 2  and the N-atom to which they are attached, a 5-membered ring, is a residue of an amino acid, in particular a proteinogenic amino acid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkyl carboxylic acid.

The present invention relates the preparation, purification andisolation of acylamino acids and derivatives thereof. The invention alsorelates to stock solutions containing said acylamino acids orderivatives, which can be easily formulated into all manner of edibleproducts, such as beverages and foodstuffs.

Acylamino acids and derivatives thereof according to the general formula(I), defined hereinbelow, represent a class of taste-modifyingingredients that can be employed in a wide variety of foodstuffs,beverages and other consumable products.

The compounds may be prepared by the reaction of a fatty acid or aderivative thereof, such as a fatty acid halide or anhydride, with anamino acid, or a derivative thereof. Whereas the synthesis of thesecompounds appears quite straightforward, applicant found that thecompounds are very difficult to purify and isolate from a reactionmixture.

The compounds are valued for their taste modifying properties, as wellas the mouth feel or body they impart to flavour compositions or edibleproducts into which they are incorporated. As such, it would bedesirable if they could be easily and efficiently separated from anystarting materials, side products or solvents of a reaction mixture,which might negatively affect their taste profile. Unfortunately, thecompounds do not crystallize readily. Instead, they form an intractablesolid mass, which presents a significant technical and commercialobstacle in the path leading towards industrialization of these usefulcompounds.

There remains a need to provide a method of preparing and purifyingthese compounds, which can be easily and efficiently carried out on anindustrialized scale, and which presents the compounds in a physicalform that facilitates their subsequent incorporation into a variety offlavour compositions and edible products, such as beverages and foodstuffs.

The invention provides in a first aspect a method of isolating andrecovering a compound according to the formula (I) from a reactionmixture comprising said compound in a reaction solvent, characterized inthat, prior to removal of the reaction solvent by evaporation, anextraction solvent for the compound, having a higher boiling point thanthe reaction solvent, is added to the reaction mixture, and whereinafter separation of the compound from the reaction solvent, the compoundof formula (I) is recovered in the form of a stock solution in saidextraction solvent.

Despite the numerous possible solvents that could be employed in theisolation and purification of organic compounds from complex reactionmixtures, the selection of a suitable extraction solvent to form a stocksolution of compounds of formula (I) was not a trivial matter. Thecompounds of formula (I) possess polar groups but also a largehydrophobic chains; as such, there was no systematic relationshipbetween solvent polarity and the ability to dissolve the compounds toform appropriately concentrated solutions. Still further, any solventwith the requisite solvating properties, has to be sufficiently higherboiling than a reaction solvent in order to make separation of thecompound from the reaction solvent possible without concomitantevaporative loss of the extraction solvent. Still further, the solvent,in the levels employed in the stock solution, should not present anynegative aesthetics when employed in flavour compositions. And finally,it should not hinder further processing of the stock solution into otherphysical forms. For example, should it be desirable to further process acompound of formula (I) in stock solution, into a powder form, the stocksolution solvent should permit the association of the stock solutionwith various constituents used in the formation of dry powders, such asbulking agents, surfactants, water and the like, in order to facilitatethe powder-forming process, and the presence of the solvent should nothave a deleterious effect on the physical properties of the powder soformed.

In a particular embodiment of the present invention, the extractionsolvent is an organic solvent that is able to produce an at least 0.1%,more particularly an up to 5%, more particularly an up to 10%, stillmore particular an up to 15%, still more particularly an up to 20%,still more particularly an up to 25%, still more particularly an up to30% stock solution of a compound of formula (I). The skilled person willappreciate that a stock solution in a range of concentrations between0.1% to about 30% falls within the purview of the present invention. Thepresent invention also contemplates any range between these values.

In a particular embodiment of the present invention, the extractionsolvent may be selected from a water-miscible organic solvent selectedfrom the group consisting of water-miscible alcohols, such as ethanol,glycerol, ethylene glycol, propylene glycol, or derivatives thereof,such as triacetine; or miglyol.

In a particularly preferred embodiment of the present invention theextraction solvent is propylene glycol.

Propylene glycol, is practically tasteless and so is acceptable for usein flavour applications. However, it was somewhat surprisingly able todissolve sufficient quantities of the compounds of formula (I) in orderto make appropriately concentrated stock solutions of the compounds thatcould be conveniently incorporated into flavour bases.

The invention provides in another of its aspects a method of forming astock solution comprising the steps of isolating and recovering acompound according to the formula (I) from a reaction mixture comprisingsaid compound in a reaction solvent, characterized in that, prior toremoval of the reaction solvent by evaporation, an extraction solventfor the compound, having a higher boiling point than the reactionsolvent, is added to the reaction mixture, and wherein after separationof the compound from the reaction solvent, the compound of formula (I)is recovered in the form of a stock solution in said extraction solvent.

In isolating a compound of formula (I) in the extraction solvent, itmight be necessary or desirable to further purify the solution ofcompound of formula (I) in the extraction solvent. This can be achievedby adding to said solution, a non-polar solvent into which contaminantspresent in the solution can partition. Typical of non-polar solventsinclude heptane, hexane, pentane, cyclohexane, or aromatics such astoluene or benzene. Accordingly, it is desirable if the extractionsolvent for the compounds of formula (I), either alone or with theaddition of a small amount of water, e.g. about 5% water, are immisciblewith, and will form a two-phase system with, said non-polar solvents. Ofthe extraction solvents referred to herein, propylene glycol is aparticularly useful in this respect.

The invention provides in another of its aspects a stock solution of acompound of formula (I) in a solvent selected from the group consistingof water-miscible alcohols, such as ethanol, glycerol, ethylene glycol,propylene glycol, or derivatives thereof, such as triacetine; ormiglyol.

In a particular embodiment of the present invention there is provided astock solution of a compound of formula (I) in propylene glycol.

In a particular embodiment of the present invention there is provided anat least 5%, more particularly an at least 10%, still more particularlyan at least 15%, more particularly still an at least 25% stock solutionof a compound of formula (I).

Still more particularly, in an embodiment of the invention there isprovided an at least 5%, more particularly an at least 10%, still moreparticularly an at least 15% stock solution of a compound of formula (I)in propylene glycol.

In yet another aspect of the invention there is provided a stocksolution as herein described formed according to a method as hereindescribed.

The stock solution may contain other adjuvants. In a particularembodiment, the stock solution contains an anti-oxidant selected fromthe group consisting of vitamin C, vitamin E, rosemary extract,antrancine, butylated hydroxyanisole (BHA) and butylated hydroxytoluene(BHT). Anti-oxidants are preferably employed to prevent, orsignificantly reduce, generation of volatile off notes as a result ofdegradation of the compounds of formula (I). Anti-oxidants areparticularly preferred when the compounds of formula (I) bear a residueof an unsaturated fatty acid. Anti-oxidants are particularly preferredif the fatty acid residue contains more than 1 double bond.Determination of an effective amount of anti-oxidant is within thepurview of the skilled person, however amounts in the range of about 10ppm to 1000 ppm based on the weight of the stock solution may bepresent.

The compounds of formula (I) are amides. Synthetic procedures forforming amides are well known in the art. The compounds may be formed bythe reaction of an amino acid with a carboxylic acid derivative such asa halide, e.g. a chloride or an anhydride in the presence of a base,such as sodium hydroxide. Yield and reaction times may be improved byapplying heat to the reaction mixture.

Selection of the reaction solvent system in which to carry out thereaction may be based on solubility considerations, both of the startingmaterials and the compounds of formula (I). Consideration may also begiven to reaction solvent that will promote amide formation. A suitablereaction solvent system is water and a water-miscible organic solvent,or an organic solvent that has some solubility in water. Suitableorganic solvents include, therefore, polar ethers such astetrahydrofuran (THF), 2-methyl-tetrahydrofuran (MeTHF), dimethoxyethane(DME), dimethylisosorbide (DMIS), or mixtures of these ethers.

It is particularly preferred if the water-miscible organic solvent inwhich the reaction is carried out will phase-separate if a salt is addedto the reaction mixture once the reaction to form a compound of formula(I) has reached completion. In this way, the aqueous saline phase andany aqueous-soluble impurities or unreacted starting materials can beseparated and discarded or recycled as appropriate.

In a particular embodiment of the present invention, a method of forminga compound of formula (I) proceeds according to the following procedure:

A fatty acid derivative, such as an acid chloride or acid anhydride, isadded to a solution of amino acid in a water/water-miscible organicsolvent, in the presence of a base. After stirring for 1 to 2 hours, thereaction mixture is acidified and a two-phase mixture is formed. Thephases are separated and the aqueous phase is washed with an organicsolvent. The organic solvent washings are combined with thewater-miscible organic solvent and the combined solvent solution iswashed with brine before being concentrated by evaporation. Anextraction solvent having a boiling point higher than the concentratedsolvents is added and the lower boiling solvents are removed byevaporation. Optionally, water is added to the extraction solvent andthe water/solvent mixture is extracted with a non-polar solvent, such asheptane, in order to remove any unreacted fatty acid derivatives.Thereafter, the extraction solvent may be concentrated to form a stocksolution of the present invention.

The compounds of formula (I) are represented by the general formula

whereinR₁ together with the carbonyl group to which it is attached is a residueof a carboxylic acid, more particular a saturated or unsaturated fattyacid, and NR₂R₃, in which R₃ is H or together with R₂ and the N-atom towhich they are attached, a 5-membered ring, is a residue of an aminoacid, in particular a proteinogenic amino acid, ornithine,gamma-aminobutyric acid or beta alanine, or a 1-amino cycloalkylcarboxylic acid.

The compounds of formula (I) may also be presented in the form of theiredible salts. Edible salts include those typically employed in the foodand beverage industry and include chlorides, sulphates, phosphates,gluconates, sodium, citrates, carbonates, acetates and lactates. All ofthe compounds of formula (I) described hereinabove and hereinbelow, mayalso be in the form their esters, that is, the carboxylic acidfunctionality of the amino acid moiety, may be esterified.

The proteinogenic amino acids are alanine (Ala), cysteine (Cys),aspartic acid (Asp), phenylalanine (Phe), glutamic acid (Glu), histidine(His), isoleucine (Ile), lysine (Lys), leucine (Leu), methionine (Met),asparagines (Asn), glutamine (Gln), arginine (Arg), serine (Ser),theronine (Thr), valine (Val), tryptophan (Trp), tyrosine (Tyr), proline(Pro) or glycine (Gly).

The three letter codes in parentheses are common abbreviations used inrelation to the amino acids and they shall be used henceforth.

The carboxylic acids can likewise be represented by abbreviations.Henceforth, the carboxylic acid residues may be referred to by theabbreviation Cn, wherein “n” represents the number of carbon atoms inthe residue. For example, the residue of an 18 carbon acid may beabbreviated as C18. Still further, if the 18 carbon acid is saturated,e.g. stearic acid. It may be abbreviated as C18:0 (because it containszero double bonds), whereas an 18 carbon acid having one doublebond—e.g. oleic acid—may be abbreviated as C18:1. Still further, if theC18 acid has a single double bond in the cis configuration, then it canbe abbreviated as C18:1c. Similarly, if the double bond was in the transconfiguration, then the abbreviation becomes C18:1t.

The compounds of formula (I) can also be represented in terms of theseabbreviations. For example, the compound of formula (I) consisting of aresidue of a C18 carboxylic acid and a residue of the amino acid Prolinecan be represented by the abbreviation C18-Pro. For simplicity thecompounds of formula (I) henceforth may be represented in thisabbreviated form.

As is evident from the above formula (I), an amino nitrogen atom on theamino acid residue is bound to a carbonyl carbon atom of the carboxylicacid residue to form an amide linkage. Some amino acids (ornithine andLysine) have more than one amine groups, and the amide linkage can beformed at any of these amino groups.

In a particular embodiment of the present invention the carboxylic acidresidue is a residue of a fatty acid.

The fatty acid residue may be the residue of a C8 to C22 fatty acid,which may be saturated or unsaturated. The fatty acid may be mammalianor non-mammalian. A mammalian fatty acid is a natural or synthetic fattyacid that is identical in structure to one naturally produced in amammal, including, but not limited to, myristic acid, palmitic acid,stearic acid, oleic acid, linoleic acid, linolenic acid, eicosatrienoicacid, arachidonic acid, eicosapentenoic acid, and docosatetraenoic acid.A non-mammalian fatty acid is a natural or synthetic fatty acid notnormally produced by a mammal, including, but not limited to,pentadecanoic acid; heptadecanoic acid; nonadecanoic acid; heneicosanoicacid; 9-trans-tetradecenoic acid; 10-trans-pentadecenoic acid;9-trans-hexadecenoic acid; 10-trans-heptadecenoic acid;10-trans-heptadecenoic acid; 7-trans-nonadecenoic acid;10,13-nonadecadienoic acid; 11-trans-eicosenoic acid; and12-transhenicosenoic acid.

The fatty acid residues may be saturated or unsaturated. If they areunsaturated, it is preferred that they have 1, 2 or 3 double bonds,which may in cis- or trans-configuration. More particularly, thepreferred fatty acid residues are C16 to C18, and may be saturated orunsaturated.

The skilled person will appreciate, however, that natural sources ofthese fatty acids, for example almond oil, avocado oil, castor oil,coconut oil, corn oil, cottonseed oil, olive oil, peanut oil, rice branoil, safflower oil, sesame oil, soybean oil, sunflower oil, palm oil andcanola oil, each consist of a complex mixture of fatty acids. Forexample, safflower oil is predominately a source of the C18:2 linoleicacid, nevertheless it may contain other fatty acids, such as linolenicacid (C18:3) and palmitic acid (C16:0), amongst others. Accordingly,reference herein to a compound containing a particular fatty acidresidue, for example a residue of C18 fatty acid, may be a reference toa pure, or substantially pure C18 fatty acid residue, or it may relateto a mixture of fatty acid residues with the predominant residue being aC18 residue.

The presentation of compounds of formula (I) in the form of stocksolutions is particularly preferred for those compounds having arelatively long fatty acid chain, for example those compounds formedfrom C16 to C22 fatty acids, more particularly C16 to C18 fatty acids.Stock solutions are also particularly preferred for compounds formedfrom fatty acids of natural origin, i.e. fatty acids contained innatural oils that exist in the form of mixtures of fatty acids, ratherthan the fatty acids in pure form. Stock solutions are also preferredfor fatty acids that are unsaturated.

Compounds of formula (I) may contain chiral atoms, and as such they mayexist in racemic form, as a mixture of stereoisomers or as resolved assingle isomers. The use of the term “a compound of formula (I)” mayrefer to both mixtures of isomers or resolved single isomers.

In particular, the compounds of formula (I) may contain the residue ofD- or L-amino acids.

In an embodiment of the the present invention the compounds of formula(I) are represented by the formula

whereinR₁, is hereinabove defined, andn is 1, 2, 3 or 4.

The preferred compounds are those wherein “n” is 1.

The amino acid residue disclosed in the above formula may be abbreviatedas “ACCA”.

The compounds include C8-ACCA, C9-ACCA, C10-ACCA, C12-ACCA, C14-ACCA,C16-ACCA, C18-ACCA, C20-ACCA and C22-ACCA.

The compounds include C8-ACCA, C9-ACCA, C10-ACCA, C12-ACCA, C14-ACCA,C16-ACCA, C18-ACCA, C20-ACCA and C22-ACCA, wherein the carboxylic acidresidue is saturated.

The compounds include C8-ACCA, C9-ACCA, C10-ACCA, C12-ACCA, C14-ACCA,C16-ACCA, C18-ACCA, C20-ACCA and C22-ACCA, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

The compounds include those specified above wherein the cycloalkane ringin the amino acid residue is cyclopropane (n=1).

Particularly preferred compounds are N-palmitoyl 1-amino-cyclopropylcarboxylic acid (C16:0-ACCA), N-stearoyl 1-amino-cyclopropyl carboxylicacid (C18:0-ACCA), N-linoleoyl 1-amino-cyclopropyl carboxylic acid(C18:2-ACCA), N-linolenoyl 1-amino-cyclopropyl carboxylic acid(C18:3-ACCA), N-oleoyl 1-amino-cyclopropyl carboxylic acid (C18:1-ACCA),N-(9-palmitenoyl) 1-amino-cyclopropyl carboxylic acid (C16:1-ACCA),N-decanoyl 1-amino-cyclopropyl carboxylic acid (C10:0-ACCA) andN-geranoyl 1-amino-cyclopropyl carboxylic acid (C10:2-ACCA).

In another embodiment the compounds of formula (I) are represented bythe formula

whereinR₁, is hereinabove defined, andm is 0 or 1.

It will be apparent to the person skilled in the art that when m is 1,the amino acid residue is a residue of gamma amino butyric acid (GABA),whereas when m is 0, the amino acid residue is a residue of beta-alanine(Beta Ala). Both the compounds of formula (I) wherein m is 1 and theamino acid residue is a residue of GABA, and the compounds of formula(I) wherein m is 0 and the amino acid residue is a residue ofbeta-alanine, their edible salts, as well as their use in edibleproducts, are all embodiments of the present invention.

These compounds are particularly useful to incorporate into an edibleproduct to impart a remarkable mouthfeel, body and enhanced fatperception; or an enhanced umami or salt taste; or a cooling andrichness. They are particularly useful in applications low in fat, saltand umami. They are also useful in fat-free formulations such asbeverages and oral care applications. They also find use in dairyapplications and in vanilla, cocoa and chocolate.

The compounds include C8-GABA, C9-GABA, C10-GABA, C12-GABA, C14-GABA,C16-GABA, C18-GABA, C20-GABA and C22-GABA.

The compounds include C8-GABA, C9-GABA, C10-GABA, C12-GABA, C14-GABA,C16-GABA, C18-GABA, C20-GABA and C22-GABA, wherein the carboxylic acidresidue is saturated.

The compounds include C8-GABA, C9-GABA, C10-GABA, C12-GABA, C14-GABA,C16-GABA, C18-GABA, C20-GABA and C22-GABA, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds include C10-GABA, C12-GABA, moreparticularly C12:1-GABA, C14-GABA, C16-GABA, more particularlyC16:1-GABA, C18-GABA, more particularly C18:1-GABA, still moreparticularly C18:1c-GABA and C18:1t-GABA. Most preferred is a compoundC18:2-GABA.

The compounds include C8-Beta Ala, C9-Beta Ala, C10-Beta Ala, C12-BetaAla, C14-Beta Ala, C16-Beta Ala, C18-Beta Ala, C20-Beta Ala and C22-BetaAla.

The compounds include C8-Beta Ala, C9-Beta Ala, C10-Beta Ala, C12-BetaAla, C14-Beta Ala, C16-Beta Ala, C18-Beta Ala, C20-Beta Ala and C22-BetaAla, wherein the carboxylic acid residue is saturated.

The compounds include C8-Beta Ala, C9-Beta Ala, C10-Beta Ala, C12-BetaAla, C14-Beta Ala, C16-Beta Ala, C18-Beta Ala, C20-Beta Ala and C22-BetaAla, wherein the carboxylic acid residue is unsaturated and contains 1,2 or 3 double bonds. The double bonds may be in cis-configuration,trans-configuration or a mixture of cis- and trans-configuration.

A preferred compound is C18:2-Beta Ala.

In another embodiment the compounds of formula (I) are represented bythe formula

whereinR₁, is hereinabove defined,R₃ is hydrogen or methyl, andR₄ is methyl, ethyl or iso-propyl.

Particular compounds are those in which R₃ is hydrogen and R₄ isiso-propyl; R₃ is methyl and R₄ is methyl; and R₃ is methyl and R₄ isethyl. The skilled person will appreciate that the amino acid residue inwhich R₃ is hydrogen and R₄ is iso-propyl is the residue of Leucine(Leu); whereas the amino acid residue in which R₃ is methyl and R₄ ismethyl is the residue of Valine (Val); and the amino acid residue inwhich R₃ is methyl and R₄ is ethyl is the residue of iso-Leucine (Ile).

The compounds in which R₃ is hydrogen and R₄ is iso-propyl; R₃ is methyland R₄ is methyl; and R₃ is methyl and R₄ is ethyl, as well as their usein edible products, are all embodiments of the present invention.

These compounds are particularly useful to enhance authentic fruitprofiles, They may also find use in fruit flavoured milk, yoghurt andice creams.

The compounds include C8-Leu, C9-Leu, C10-Leu, C12-Leu, C14-Leu,C16-Leu, C18-Leu, C20-Leu and C22-Leu.

The compounds include C8-Leu, C9-Leu, C10-Leu, C12-Leu, C14-Leu,C16-Leu, C18-Leu, C20-Leu and C22-Leu, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Leu, C9-Leu, C10-Leu, C12-Leu, C14-Leu,C16-Leu, C18-Leu, C20-Leu and C22-Leu, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particular compounds bearing the Leu residue includeN-palmitenoyl-L-leucine, N-palmitoyl-L-leucine, N-linolenoyl-L-leucine,N-linoleoyl-L-leucine and N-oleoyl-L-leucine.

The compounds include C8-Ile, C9-Ile, C10-Ile, C12-Ile, C14-Ile,C16-Ile, C18-Ile, C20-Ile and C22-Ile.

The compounds include C8-Ile, C9-Ile, C10-Ile, C12-Ile, C14-Ile,C16-Ile, C18-Ile, C20-Ile and C22-Ile, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Ile, C9-Ile, C10-Ile, C12-Ile, C14-Ile,C16-Ile, C18-Ile, C20-Ile and C22-Ile, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

A particularly preferred compound bearing the Ile residue isN-oleoyl-Ile.

The compounds include C8-Val, C9-Val, C10-Val, C12-Val, C14-Val,C16-Val, C18-Val, C20-Val and C22-Val.

The compounds include C8-Val, C9-Val, C10-Val, C12-Val, C14-Val,C16-Val, C18-Val, C20-Val and C22-Val, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Val, C9-Val, C10-Val, C12-Val, C14-Val,C16-Val, C18-Val, C20-Val and C22-Val, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Val residue includeN-palmitenoyl-L-valine, N-palmitoyl-L-valine, N-linolenoyl-L-valine,N-linoleoyl-L-valine and N-oleoyl-L-valine.

In another embodiment the compounds of formula (I) are represented bythe formula

whereinR_(L) is hereinabove defined.

The skilled person will appreciate that the amino acid residue in thecompounds defined above is the proline residue (Pro).

These compounds are particularly effective to enhance juiciness andtypical citrus authenticity. They find use particularly in powdered softdrinks and beverages, and also in dairy applications, such as fruitflavoured milk, yoghurt and ice creams.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Pro, C9-Pro, C10-Pro, C12-Pro, C14-Pro,C16-Pro, C18-Pro, C20-Pro and C22-Pro, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Pro residue N-geranoyl-Pro,N-palmitoyl-Pro, N-palmiteneoyl-Pro, N-stearoyl-Pro, N-linoleoyl-Pro andN-linolenoyl-Pro.

In another embodiment of the invention, the compounds of formula (I) arerepresented by the formula

whereinR₁, is hereinabove defined,

X is OH or NH₂ and P is 0 or 1.

The skilled person will appreciate that when p is 0 and X is OH, theamino acid residue set forth in the above formula is a residue ofaspartic acid, whereas when p is 1, and X is OH the residue is that ofglutamic acid, whereas when p is 0 and X is NH₂, the residue is that ofasparagine (Asn), and when p is 1 and X is NH₂, the residue is that ofglutamine (GM).

The compounds bearing an aspartic acid residue, the compounds bearing aglutamic acid residue, the compounds bearing an asparagine residue, andthe compounds bearing a glutamine residue, as well as their ediblesalts, and their use in edible products, each represent particularembodiments of the present invention.

These compounds are particularly useful to enhance savoury character,mouthfeel and overall flavour performance, juiciness and salivation.They may find use in low salt, low umami and low fat as well as fruitflavour drinks as well as dairy applications.

The compounds include C8-Glu, C9-Glu, C10-Glu, C12-Glu, C14-Glu,C16-Glu, C18-Glu, C20-Glu and C22-Glu.

The compounds include C8-Glu, C9-Glu, C10-Glu, C12-Glu, C14-Glu,C16-Glu, C18-Glu, C20-Glu and C22-Glu, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Glu, C9-Glu, C10-Glu, C12-Glu, C14-Glu,C16-Glu, C18-Glu, C20-Glu and C22-Glu, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Glu residue includeN-geranoyl-Glu, N-palmitoyl-Glu, N-palmitenoyl-Glu, N-stearoyl-Glu,N-linoleoyl-Glu and N-linolenoyl-Glu.

The compounds include C8-Asp, C9-Asp, C10-Asp, C12-Asp, C14-Asp,C16-Asp, C18-Asp, C20-Asp and C22-Asp.

The compounds include C8-Asp, C9-Asp, C10-Asp, C12-Asp, C14-Asp,C16-Asp, C18-Asp, C20-Asp and C22-Asp, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Asp, C9-Asp, C10-Asp, C12-Asp, C14-Asp,C16-Asp, C18-Asp, C20-Asp and C22-Asp, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Asp residue includeN-geranoyl-Asp, N-palmitoyl-Asp, N-palmitenoyl-Asp, N-stearoyl-Asp,N-linoleoyl-Asp and N-linolenoyl-Asp.

The compounds include C8-Gln, C9-Gln, C10-Gln, C12-Gln, C14-Gln,C16-Gln, C18-Gln, C20-Gln and C22-Gln.

The compounds include C8-Gln, C9-Gln, C10-Gln, C12-Gln, C14-Gln,C16-Gln, C18-Gln, C20-Gln and C22-Gln, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Gln, C9-Gln, C10-Gln, C12-Gln, C14-Gln,C16-Gln, C18-Gln, C20-Gln and C22-Gln, wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Gln residue includeN-geranoyl-Gln, N-palmitoyl-Gln, N-palmitenoyl-Gln, N-stearoyl-Gln,N-linoleoyl-Gln and N-linolenoyl-Gln.

The compounds include C8-Asn, C9-Asn, C10-Asn, C12-Asn, C14-Asn,C16-Asn, C18-Asn, C20-Asn and C22-Asn.

The compounds include C8-Asn, C9-Asn, C10-Asn, C12-Asn, C14-Asn,C16-Asn, C18-Asn, C20-Asn and C22-Asn, wherein the carboxylic acidresidue is saturated.

The compounds C8-Asn, C9-Asn, C10-Asn, C12-Asn, C14-Asn, C16-Asn,C18-Asn, C20-Asn and C22-Asn, wherein the carboxylic acid residue isunsaturated and contains 1, 2 or 3 double bonds. The double bonds may bein cis-configuration, trans-configuration or a mixture of cis- andtrans-configuration.

Particularly preferred compounds bearing the Asn residue includeN-geranoyl-Asn, N-palmitoyl-Asn, N-palmitenoyl-Asn, N-stearoyl-Asn,N-linoleoyl-Asn and N-linolenoyl-Asn.

In another embodiment the compounds of formula (I) are represented bythe formula

whereinR₁, is hereinabove defined.

The skilled person will appreciate that in the above formula the aminoacid residue is the residue of methionine (Met).

These compounds are particularly effective to enhance juiciness andsalivation, as well as the authenticity of fruits. They also are usefulin soft drinks applications for their masking properties.

The compounds include C8-Met, C9-Met, C10-Met, C12-Met, C14-Met,C16-Met, C18-Met, C20-Met and C22-Met.

The compounds include C8-Met, C9-Met, C10-Met, C12-Met, C14-Met,C16-Met, C18-Met, C20-Met and C22-Met, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Met, C9-Met, C10-Met, C12-Met, C14-Met,C16-Met, C18-Met, C20-Met and C22-Met wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Met residue includeN-geranoyl-Met, N-palmitoyl-Met, N-palmitenoyl-Met, N-stearoyl-Met,N-linoleoyl-Met and N-linolenoyl-Met.

In another embodiment the compounds of formula (I) are represented bythe formula

whereinR₁, is hereinabove defined.

The skilled person will appreciate that in the above formula the aminoacid residue is the residue of serine (Ser).

These compounds find particular use in low salt, umami and fat, fruitflavoured beverages and/or dairy applications.

The compounds include C8-Ser, C9-Ser, C10-Ser, C12-Ser, C14-Ser,C16-Ser, C18-Ser, C20-Ser and C22-Ser.

The compounds include C8-Ser, C9-Ser, C10-Ser, C12-Ser, C14-Ser,C16-Ser, C18-Ser, C20-Ser and C22-Ser, wherein the carboxylic acidresidue is saturated.

The compounds include C8-Ser, C9-Ser, C10-Ser, C12-Ser, C14-Ser,C16-Ser, C18-Ser, C20-Ser and C22-Ser wherein the carboxylic acidresidue is unsaturated and contains 1, 2 or 3 double bonds. The doublebonds may be in cis-configuration, trans-configuration or a mixture ofcis- and trans-configuration.

Particularly preferred compounds bearing the Ser residue includeN-palmitoyl-Ser, N-palmitenoyl-Ser, N-stearoyl-Ser, N-linoleoyl-Ser andN-linolenoyl-Ser.

Other compounds useful in the present invention include:

N-octanoyl-L-phenylalanine, N-eicosanoyl-L-phenylalanine,N-palmitoleoyl-L-phenylalanine, N-palmitoyl-L-phenylalanine,N-linolenoyl-L-phenylalanine, N-linoleoyl-L-phenylalanine,N-oleoyl-L-phenylalanine, N-SDA-L-phenylalanine, N-DPA-L-phenylalanine,and N-tetracosahexaenoyl-L-phenylalanine;

N-palmitoyl-L-alanine, N-linolenoyl-L-alanine, N-linoleoyl-L-alanine;N-palmitoyl-L-tyrosine, N-linoleoyl-L-tyrosine, N-oleoyl-L-tyrosine,N-linolenoyl-L-tyrosine; N-palmitoyl-L-tryptophan,N-linolenoyl-L-tryptophan, N-linoleoyl-L-tryptophan; and

N-linoleoyl-glycine.

The stock solutions containing compounds of formula (I) can impartorganoleptic properties to flavour compositions and edible products towhich they are added. In particular, they impart highly intense,authentic and harmonious flavour, and a roundness and fullness toflavour compositions and edible products containing them.

This finding was surprising considering that when the compoundsthemselves merely exhibit a disappointing, faintly fatty taste profile.As such, they appeared to be quite unsuitable for use in flavourapplications. Only their combination with flavour co-ingredients and thejudicious selection of their usage levels was it possible to discoverthe remarkable organoleptic properties of these compounds. Their effecton edible products is quite unusual in that they actually complement,lift or accentuate the essential or authentic flavour and mouth feelcharacteristics of the foods or beverages in which they areincorporated. Accordingly, the stock solutions containing compounds offormula (I) find utility in a broad spectrum of applications in the foodand beverage industry, as well as in health and wellness.

Accordingly, the invention provides in another of its aspects, a methodof conferring flavour and/or mouthfeel to, or improving taste and/ormouthfeel of a flavour composition or edible product, which methodcomprises adding to said composition or product a stock solutioncontaining a compound of formula (I) as defined herein.

The organoleptic effects are observed when the stock solutionscontaining compounds of formula (I) are incorporated into flavourcompositions and edible products containing one or more flavourco-ingredients.

The flavour co-ingredients may be sugars, fats, salt (e.g. sodiumchloride), MSG, calcium ions, phosphate ions, organic acids, proteins,purines and mixtures thereof.

In a particular embodiment, sugars are present in amounts of 0.001% to90%, more particularly 0.001% to 50%, still more particularly 0.001% to20% based on the total weight of an edible product.

In a particular embodiment, fats are present in amounts of 0.001% to100%, more particularly 0.001% to 80%, more particularly 0.001% to 30%,still more particularly 0.001% to 5% based on the total weight of anedible product.

In a particular embodiment, salt (e.g. sodium chloride) is present inamounts of 0.001% to 20%, more particularly 0.001% to 5% based on thetotal weight of an edible product.

In a particular embodiment, MSG is present in amounts of 0.001% to 2%based on the total weight of an edible product.

In a particular embodiment, calcium is present in amounts of 0.001% to50% more particularly 0.001% to 20%, still more particularly 0.001% to1% based on the total weight of an edible product.

In a particular embodiment, organic acids are present in amounts of0.001% to 10%, more particularly 0.001% to 7% based on the total weightof an edible product.

Types of organic acids include citric, malic, tartaric, fumaric, lactic,acetic and succinic.

Types of edible products containing organic acids include beverages,such as carbonated soft drink beverages, still beverages, Juices,powdered soft drinks, liquid concentrates, alcoholic beverages andfunctional beverages.

In a particular embodiment, phosphorus is present in an amount up to0.5% by weight of an edible product. Typically phosphorus will bepresent as a phosphate or as phosphoric acid.

In a particular embodiment, purines are present in an amount up to 0.5%by weight of an edible product. The term “purines” includeribonucleotides such as IMP and GMP.

In preparing the flavour compositions of the present invention, thestock solutions may be simply mixed into a flavour composition, or itmay be further diluted into other solvents, such as triacetin, miglyolor other solvent useful in food stuffs and beverages.

However, it might be desirable to further process the stock solutions,for example, drying them in a dispersive evaporative process, such asspray drying, fluid bed drying, drum drying, film drying and vacuumdrying order to present the compounds of formula (I) into a powderedform.

Accordingly, in another aspect of the present invention, there isprovided a powder formulation comprising a compound of formula (I)formed from a stock solution as defined herein.

In a particular embodiment, the powder is formed according to a spraydrying process.

Spray dried powders according to the invention may be prepared accordingto methods and apparatus known in the art for producing powders on anindustrial scale. A particularly suitable method is spray drying. Spraydrying techniques and apparatus are well known in the art and need nodetailed discussion herein. The spray drying techniques, apparatus andmethods described in US2005/0031769 and US2013/0022728, as well as thosetechniques, apparatus and methods described in those documents aresuitable for producing powder compositions of the present invention andare herein incorporated by reference in their entirety.

In particular, powder compositions may be prepared by mixing the stocksolution with a suitable carrier material and optionally additionalflavour co-ingredients, and optionally a surfactant, and spraying theresultant mixture a conventional spray dry apparatus as referred tohereinabove.

The stock solutions of the present invention would not be conventionallyconsidered as the most suitable materials to employ in a dryingoperation. The solvents employed in forming the stock solutions, and inparticular the water-miscible alcohols, can affect the powder quality ofa finished dried powder. In particular, the use of such solvents cancause caking of powders. The use of propylene glycol can be particularlyproblematic in this regard. Nevertheless, applicant found that employingsufficiently concentrated stock solutions, such as about 5 to about 30%,more particularly about 10 to 15% solutions, it was possible to obtaingood powder quality.

The applicant also found that selection of the bulking material (orcarrier material as it is also referred to) used in the composition tobe dried can also improve the quality of the powder qualitynotwithstanding the use of these solvents in the stock solution.

The carrier material may be chosen from modified starches, such asoctenyl succinic anhydride (OSA), starch and maltodextrins; gum Arabic,modified gum Arabic, dextrins, animal and vegetable derived proteins,such as gelatin, soy, pea, whey and milk proteins; low molecular weightsugars, such as glucose, fructose, sucrose, maltose, maltotriose,lactose, and the like; polyols; such as mannitol, xylitol, sorbitol,maltitol, lactitol; and salts of food acids, such as magnesium citrate.

Preferred carrier materials are those having relatively high Tg, Acarrier material having a Tg of between 80 and 120 degrees centigrademay be considered high Tg carrier materials. Similarly, a carriermaterial equilibrated under conditions of ambient temperature and 50%relative humidity, which exhibits a Tg of at least 40 degreescentigrade, may be considered a high Tg carrier material. Tg can bemeasured using DSC techniques known generally in the art. Suitableequilibration conditions are described in the examples hereinbelow.

Exemplary high Tg carrier materials are the modified starches, proteinsand gum Arabic. Particular high Tg carriers include maltodextrins havinga dextrose equivalent (DE) of about 3 to 25, more particularly 3 to 20.

Accordingly, in another aspect of the present invention there isprovided a dried powder formulation comprising a compound of formula(I), and a carrier material selected from the group comprising any ofthe high Tg carrier materials referred to hereinabove, more particular ahigh Tg carrier referred to hereinabove that is a maltodextrin havingdextrose equivalent of 3 to 25, more particularly 3 to 20, or gumArabic.

Dried powders formed from high Tg carrier materials are physicallystable, that is, they are not prone to caking.

The compound of formula (I) may be loaded onto a dried powder in anydesired amount. However, it is preferred if a compound of formula (I) isloaded in an amount present in a dried powder in an amount of about 0.1up to about 10% by weight, more particularly about 0.1 to 5% by weight,still more particularly 0.1 to 3% by weight, e.g. 1.5% by weight, basedon the total weight of the powder. The loading is determined by thesolubility of the compound of formula (I) in the stock solution, as wellas the need to keep the concentration of the stock solution solvent aslow as possible in the spray drying composition to prevent or reduce theincidence of subsequent issues with powder caking.

The compounds of formula (I), for example, in the form of a stocksolution, or in the form of a dried powder, may be incorporated into anedible product, alone, or in the form of a flavour compositioncomprising one or more flavour co-ingredients.

A flavour composition comprising a stock solution or dried powdercontaining a compound according to the formula (I) forms a furtheraspect of the present invention.

In an embodiment of the present invention, the flavour compositioncomprises a compound of formula (I) and at least one flavourco-ingredient.

In a particular embodiment of the present invention the flavourcomposition comprises:

-   -   i) a compound according to formula (I);    -   ii) at least one flavour co-ingredient;    -   iii) optionally a carrier material; and    -   iv) optionally at least one adjuvant.

The term “flavour co-ingredient” is an ingredient that is able tocontribute or impart or modify in a positive or pleasant way the tasteof a flavour composition or an edible product.

All manner of flavour co-ingredients may be employed in a flavourcomposition or edible product according to the present invention,including, but not limited to natural flavours, artificial flavours,spices, seasonings, and the like. Flavour co-ingredients includesynthetic flavour oils and flavouring aromatics and/or oils, oleoresins,essences, distillates, and extracts derived from plants, leaves,flowers, fruits, and so forth, and combinations comprising at least oneof the foregoing.

Flavour oils include spearmint oil, cinnamon oil, oil of wintergreen(methyl salicylate), peppermint oil, Japanese mint oil, clove oil, bayoil, anise oil, eucalyptus oil, thyme oil, cedar leaf oil, oil ofnutmeg, allspice, oil of sage, mace, oil of bitter almonds, and cassiaoil; useful flavouring agents include artificial, natural and syntheticfruit flavours such as vanilla, and citrus oils including lemon, orange,lime, grapefruit, yazu, sudachi, and fruit essences including apple,pear, peach, grape, blueberry, strawberry, raspberry, cherry, plum,prune, raisin, cola, guarana, neroli, pineapple, apricot, banana, melon,apricot, ume, cherry, raspberry, blackberry, tropical fruit, mango,mangosteen, pomegranate, papaya and the like.

Additional exemplary flavours imparted by a flavouring agent include amilk flavour, a butter flavour, a cheese flavour, a cream flavour, and ayogurt flavour; a vanilla flavour; tea or coffee flavours, such as agreen tea flavour, an oolong tea flavour, a tea flavour, a cocoaflavour, a chocolate flavour, and a coffee flavour; mint flavours, suchas a peppermint flavour, a spearmint flavour, and a Japanese mintflavour; spicy flavours, such as an asafetida flavour, an ajowanflavour, an anise flavour, an angelica flavour, a fennel flavour, an allspice flavour, a cinnamon flavour, a chamomile flavour, a mustardflavour, a cardamom flavour, a caraway flavour, a cumin flavour, a cloveflavour, a pepper flavour, a coriander flavour, a sassafras flavour, asavoury flavour, a Zanthoxyli Fructus flavour, a perilla flavour, ajuniper berry flavour, a ginger flavour, a star anise flavour, ahorseradish flavour, a thyme flavour, a tarragon flavour, a dillflavour, a capsicum flavour, a nutmeg flavour, a basil flavour, amarjoram flavour, a rosemary flavour, a bayleaf flavour, and a wasabi(Japanese horseradish) flavour; a nut flavour such as an almond flavour,a hazelnut flavour, a macadamia nut flavour, a peanut flavour, a pecanflavour, a pistachio flavour, and a walnut flavour; alcoholic flavours,such as a wine flavour, a whisky flavour, a brandy flavour, a rumflavour, a gin flavour, and a liqueur flavour; floral flavours; andvegetable flavours, such as an onion flavour, a garlic flavour, acabbage flavour, a carrot flavour, a celery flavour, mushroom flavour,and a tomato flavour.

In some embodiments, said flavour co-ingredients include aldehydes andesters such as cinnamyl acetate, cinnamaldehyde, citral diethylacetal,dihydrocarvyl acetate, eugenyl 49 formate, p-methylamisol, and so forthcan be used. Further examples of aldehyde flavourings includeacetaldehyde (apple), benzaldehyde (cherry, almond), anisic aldehyde(licorice, anise), cinnamic aldehyde (cinnamon), citral, i.e.,alpha-citral (lemon, lime), neral, i.e., beta-citral (lemon, lime),decanal (orange, lemon), ethyl vanillin (vanilla, cream), heliotrope,i.e., piperonal (vanilla, cream), vanillin (vanilla, cream), alpha-amylcinnamaldehyde (spicy fruity flavours), butyraldehyde (butter, cheese),valeraldehyde (butter, cheese), citronellal (modifies, many types),decanal (citrus fruits), aldehyde C-8 (citrus fruits), aldehyde C-9(citrus fruits), aldehyde C-12 (citrus fruits), 2-ethyl butyraldehyde(berry fruits), hexenal, i.e., trans-2 (berry fruits), tolyl aldehyde(cherry, almond), veratraldehyde (vanilla), 2,6-dimethyl-5-heptenal,i.e., melonal (melon), 2,6-dimethyloctanal (green fruit), and2-dodecenal (citrus, mandarin), and the like.

Further examples of other flavour co-ingredients can be found in“Chemicals Used in Food Processing”, publication 1274, pages 63-258, bythe National Academy of Sciences.

Flavour co-ingredients can also include salt tastants, umami tastants,and savoury flavour compounds. Non limiting examples include: NaCl, KCl,MSG, guanosine monophosphate (GMP), inosin monophospahte (IMP),ribonucleotides such as disodium inosinate, disodium guanylate,N-(2-hydroxyethyl)-lactamide, N-lactoyl-GMP, N-lactoyl tyramine, gammaamino butyric acid, allyl cysteine,1-(2-hydroxy-4-methoxylphenyl)-3-(pyridine-2-yl)propan-1-one, arginine,potassium chloride, ammonium chloride, succinic acid,N-(2-methoxy-4-methyl benzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,Niheptan-4-yl)benzo(D)(1,3)dioxole-5-carboxamide,N-(2,4-dimethoxybenzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(2-methoxy-4-methyl benzyl)-N′-2(2-(5-methyl pyridin-2-yl)ethyl)oxalamide, cyclopropyl-E,Z-2,6-nonadienamide.

In particular embodiments of the present invention, the flavourco-ingredient is selected from the compounds and compositions disclosedin WO2005102701, WO2006009425, WO2005096843, WO2006046853 andWO2005096844, all of which references are herein incorporated byreference in their entirety.

Flavour co-ingredients may include known salt tastants, umami tastants,and savoury flavour compounds. Non limiting examples include: NaCl, KCl,MSG, guanosine monophosphate (GMP), inosin monophospahte (IMP),ribonucleotides such as disodium inosinate, disodium guanylate,N-(2-hydroxyethyl)-lactamide, N-lactoyl-GMP, N-lactoyl tyramine, gammaamino butyric acid, allyl cysteine,1-(2-hydroxy-4-methoxylphenyl)-3-(pyridine-2-yl)propan-1-one, arginine,potassium chloride, ammonium chloride, succinic acid,N-(2-methoxy-4-methyl benzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(heptan-4-yl)benzo(D)(1,3)dioxole-5-carboxamide,N-(2,4-dimethoxybenzyl)-N′-(2-(pyridin-2-yl)ethyl) oxalamide,N-(2-methoxy-4-methyl benzyl)-N′-2(2-(5-methyl pyridin-2-yl)ethyl)oxalamide, cyclopropyl-E,Z-2,6-nonadienamide.

The carrier material may be employed in flavour compositions accordingto the invention to encapsulate or to entrap in a matrix the othercomponents of the composition. The role of the carrier material may bemerely that of a processing aid or a bulking agent, or it might beemployed to shield or protect the other components from the effects ofmoisture or oxygen or any other aggressive media. The carrier materialmight also act as a means of controlling the release of flavour fromflavour compositions, or edible products.

Carrier materials may include mono, di- or trisaccharides, natural ormodified starches, hydrocolloids, cellulose derivatives, polyvinylacetates, polyvinylalcohols, proteins or pectins. Example of particularcarrier materials include sucrose, glucose, lactose, levulose, fructose,maltose, ribose, dextrose, isomalt, sorbitol, mannitol, xylitol,lactitol, maltitol, pentatol, arabinose, pentose, xylose, galactose,maltodextrin, dextrin, chemically modified starch, hydrogenated starchhydrolysate, succinylated or hydrolysed starch, agar, carrageenan, gumarabic, gum accacia, tragacanth, alginates, methyl cellulose,carboxymethyl cellulose, hydroxyethyl cellulose, hydroxypropylmethylcellulose, derivatives and mixtures thereof. Of course, the skilledaddresse with appreciate that the cited materials are hereby given byway of example and are not to be interpreted as limiting the invention.

By “adjuvant” is meant an ingredient capable of imparting additionaladded benefit to flavour compositions or edible products of the presentinvention such as a colour, light resistance, chemical stability and thelike. Suitable adjuvants include solvents (including water, alcohol,ethanol, triacetine, oils, fats, vegetable oil and miglyol), binders,diluents, disintegrating agents, lubricants, colouring agents,preservatives, antioxidants, emulsifiers, stabilisers, anti-cakingagents, and the like. In a particular embodiment, the flavourcomposition comprises an anti-oxidant. Said anti-oxidants may includevitamin C, vitamin E, rosemary extract, antrancine, butylatedhydroxyanisole (BHA) and butylated hydroxytoluene (BHT).

Examples of such carriers or adjuvants for flavour compositions oredible products may be found in for example, “Perfume and FlavourMaterials of Natural Origin”, S. Arctander, Ed., Elizabeth, N. J., 1960;in “Perfume and Flavour Chemicals”, S. Arctander, Ed., Vol. I & II,Allured Publishing Corporation, Carol Stream, USA, 1994; in“Flavourings”, E. Ziegler and H. Ziegler (ed.), Wiley-VCH Weinheim,1998, and “CTFA Cosmetic Ingredient Handbook”, J. M. Nikitakis (ed.),1st ed., The Cosmetic, Toiletry and Fragrance Association, Inc.,Washington, 1988.

Other suitable and desirable ingredients that may be employed in flavourcompositions or edible products are described in standard texts, such as“Handbook of Industrial Chemical Additives”, ed. M. and I. Ash, 2^(nd)Ed., (Synapse 2000).

Flavour compositions according to the present invention may be providedin any suitable physical form. For example, they may be in the form ofoils, emulsions or dispersions in a hydrous liquid or organic liquidsuitable for use in edible products, or solid form, such as powders.

Many of the flavour co-ingredients described herein above are volatileand/or may be sensitive to oxidative degradation, particularly whensubjected to elevated temperature, and under humid conditions.Accordingly, particular problems can arise when subjecting saidco-ingredients described above to dispersive evaporation processes suchas spray drying. A non-exhaustive list of ingredients that can beparticularly susceptible include, those ingredients containingartificial, natural or synthetic fruit flavours such as vanilla,chocolate, coffee, cocoa and citrus oil, including lemon, orange, grape,lime and grapefruit, and fruit essences including apple, pear, peach,strawberry, raspberry, cherry, plum, pineapple, apricot and the like.The volatile components of these flavour co-ingredients may include, butare not limited to, acetaldehyde, dimethyl sulfide, ethyl acetate, ethylpropionate, methyl butyrate, and ethyl butyrate. Flavour co-ingredientscontaining volatile aldehydes or esters include, e.g., cinnamyl acetate,cinnamaldehyde, citral, diethylacetal, dihydrocarvyl acetate, eugenylformate, and p-methylanisole. Further examples of volatile compoundsthat may be present as co-ingredients include acetaldehyde (apple);benzaldehyde (cherry, almond); cinnamic aldehyde (cinnamon); citral,i.e., alpha citral (lemon, lime); neral, i.e., beta citral (lemon,lime); decanal (orange, lemon); ethyl vanillin (vanilla, cream);heliotropine, i.e., piperonal (vanilla, cream); vanillin (vanilla,cream); alpha-amyl cinnamaldehyde (spicy fruity flavors); butyraldehyde(butter, cheese); valeraldehyde (butter, cheese); citronellal (modifies,many types); decanal (citrus fruits); aldehyde C-8 (citrus fruits);aldehyde C-9 (citrus fruits); aldehyde C-12 (citrus fruits); 2-ethylbutyraldehyde (berry fruits); hexenal, i.e., trans-2 (berry fruits);tolyl aldehyde (cherry, almond); veratraldehyde (vanilla);2,6-dimethyl-5-heptenal, i.e., melonal (melon); 2-6-dimethyloctanal(green fruit); and 2-dodecenal (citrus, mandarin); cherry; or grape andmixtures thereof.

Applicant surprisingly found that the inclusion of a compound of formula(I) in a powder flavour composition, it was possible to obtain flavourquality reminiscent of flavour oils. Accordingly, the invention providesin another of its aspects a method of maintaining flavour quality of apowder flavour composition comprising the step of including in saidpowder flavour composition a compound of formula (I)

The term edible product as used herein, refers to products forconsumption by a subject, typically via the oral cavity (althoughconsumption may occur via non-oral means such as inhalation), for atleast one of the purposes of enjoyment, nourishment, or health andwellness benefits. Edible products may be present in any form including,but not limited to, liquids, solids, semi-solids, tablets, capsules,lozenges, strips, powders, gels, gums, pastes, slurries, syrups,aerosols and sprays. The term also refers to, for example, dietary andnutritional supplements. Edible products include products that areplaced within the oral cavity for a period of time before beingdiscarded but not swallowed. It may be placed in the mouth before beingconsumed, or it may be held in the mouth for a period of time beforebeing discarded. An edible product as herein above defined includesproducts whose taste is modified in the manner described herein by theaddition of compounds of formula (I) or whose taste is so modified byprocessing such that it is enriched in a compound of formula (I).

Broadly, the edible products include, but are not limited to foodstuffsof all kinds, confectionery products, baked products, sweet products,savoury products, fermented products, dairy products, beverages and oralcare products.

In a particular embodiment edible products are products for consumptionby a subject, typically via the oral cavity (although consumption mayoccur via non-oral means such as inhalation), for one of the purposes ofenjoyment or nourishment.

In a more particular embodiment the edible products are products forconsumption by a subject, typically via the oral cavity (althoughconsumption may occur via non-oral means such as inhalation), for thepurpose of enjoyment. Still more particularly, they are foodstuffs andbeverages.

Exemplary foodstuffs include, but are not limited to, chilled snacks,sweet and savoury snacks, fruit snacks, chips/crisps, extruded snacks,tortilla/corn chips, popcorn, pretzels, nuts, other sweet and savourysnacks, snack bars, granola bars, breakfast bars, energy bars, fruitbars, other snack bars, meal replacement products, slimming products,convalescence drinks, ready meals, canned ready meals, frozen readymeals, dried ready meals, chilled ready meals, dinner mixes, frozenpizza, chilled pizza, soup, canned soup, dehydrated soup, instant soup,chilled soup, uht soup, frozen soup, pasta, canned pasta, dried pasta,chilled/fresh pasta, noodles, plain noodles, instant noodles, cups/bowlinstant noodles, pouch instant noodles, chilled noodles, snack noodles,dried food, dessert mixes, sauces, dressings and condiments, herbs andspices, spreads, jams and preserves, honey, chocolate spreads, nut-basedspreads, and yeast-based spreads.

Exemplary confectionery products include, but are not limited to,chewing gum (which includes sugarized gum, sugar-free gum, functionalgum and bubble gum), center-fill confections, chocolate and otherchocolate confectionery, medicated confectionery, lozenges, tablets,pastilles, mints, standard mints, power mints, chewy candies, hardcandies, boiled candies, breath and other oral care films or strips,candy canes, lollipops, gummies, jellies, fudge, caramel, hard and softpanned goods, toffee, taffy, licorice, gelatin candies, gum drops, jellybeans, nougats, fondants, combinations of one or more of the above, andedible flavour compositions incorporating one or more of the above.

Exemplary baked products include, but are not limited to, alfajores,bread, packaged/industrial bread, unpackaged/artisanal bread, pastries,cakes, packaged/industrial cakes, unpackaged/artisanal cakes, cookies,chocolate coated biscuits, sandwich biscuits, filled biscuits, savourybiscuits and crackers, bread substitutes,

Exemplary sweet products include, but are not limited to, breakfastcereals, ready-to-eat (“rte”) cereals, family breakfast cereals, flakes,muesli, other ready to eat cereals, children's breakfast cereals, hotcereals,

Exemplary savoury products include, but are not limited to, salty snacks(potato chips, crisps, nuts, tortilla-tostada, pretzels, cheese snacks,corn snacks, potato-snacks, ready-to-eat popcorn, microwaveable popcorn,pork rinds, nuts, crackers, cracker snacks, breakfast cereals, meats,aspic, cured meats (ham, bacon), luncheon/breakfast meats (hotdogs, coldcuts, sausage), tomato products, margarine, peanut butter, soup (clear,canned, cream, instant, UHT), canned vegetables, pasta sauces.

Exemplary dairy products include, but are not limited to, cheese, cheesesauces, cheese-based products, ice cream, impulse ice cream, singleportion dairy ice cream, single portion water ice cream, multi-packdairy ice cream, multi-pack water ice cream, take-home ice cream,take-home dairy ice cream, ice cream desserts, bulk ice cream, take-homewater ice cream, frozen yoghurt, artisanal ice cream, dairy products,milk, fresh/pasteurized milk, full fat fresh/pasteurized milk, semiskimmed fresh/pasteurized milk, long-life/uht milk, full fat longlife/uht milk, semi skimmed long life/uht milk, fat-free long life/uhtmilk, goat milk, condensed/evaporated milk, plain condensed/evaporatedmilk, flavoured, functional and other condensed milk, flavoured milkdrinks, dairy only flavoured milk drinks, flavoured milk drinks withfruit juice, soy milk, sour milk drinks, fermented dairy drinks, coffeewhiteners, powder milk, flavoured powder milk drinks, cream, yoghurt,plain/natural yoghurt, flavoured yoghurt, fruited yoghurt, probioticyoghurt, drinking yoghurt, regular drinking yoghurt, probiotic drinkingyoghurt, chilled and shelf-stable desserts, dairy-based desserts,soy-based desserts.

Exemplary beverages include, but are not limited to, flavoured water,soft drinks, fruit drinks, coffee-based drinks, tea-based drinks,juice-based drinks (includes fruit and vegetable), milk-based drinks,gel drinks, carbonated or non-carbonated drinks, powdered drinks,alcoholic or non-alcoholic drinks.

Exemplary fermented foods include, but are not limited to, Cheese andcheese products, meat and meat products, soy and soy products, fish andfish products, grain and grain products, fruit and fruit products.

In a particular embodiment the consumable product is selected from thegroup consisting of soy sauce, cheese, soup, hot and cold sauces,fruits, vegetables, ketchups, tea, coffee, snacks such as potato chipsor extruded snacks.

The compounds of formula (I), when added to a flavour composition and/oran edible product act to complement the flavour and/or mouthfeel torender it more delicious and authentic. The effects may be temporal orrelated to intensity, for example the compounds may act by enhancing,strengthening, softening, sharpening a flavour, or making moresalivating. The compounds of formula (I) may also affect the temporalprofile of a flavour, that is, they may affect the initial impact of aflavour, the body of a flavour, or its lingering effect.

The compounds of formula (I) may modify any aspect of the temporalprofile of taste or flavour of a flavour composition or edible product.In particular, the compounds improve mouth feel and impart more creamyand fatty sensations.

Compounds of formula (I) or flavour compositions containing same may beadded to edible products in widely carrying amounts. The amount willdepend on the nature of the edible product to be flavoured, and on thedesired effect, as well as on the nature of the ingredients present insaid flavour composition.

Preferably however, the beneficial effects attributed to the presence ofa compound of formula (I) can be achieved if the compound (or compounds,if a mixture of compounds is to be employed), employed alone or in aflavour composition, is dosed in such amounts that the compound(s)is/are present in amounts of 1 part per billion to 10 parts per millionbased on the total weight of the edible product. Whereas amounts higherthan this can be employed, the beneficial effects are considerably lessapparent and undesirable off-notes can become increasingly apparent.

Interesting organoleptic effects, e.g. salt, alcohol or coolant boostingeffects, in edible products containing salt or alcohol or coolantcompounds can be achieved when compound(s) of the formula (I) is/areemployed at levels of 1 to 100 ppb.

Interesting organoleptic effects, for example umami boosting effects, inedible products containing umami tastants can be achieved whencompound(s) of the formula (I) is/are employed at levels of 100 to 250ppb.

Interesting organoleptic effects, in particular mouthfeel boostingeffects, in edible products can be achieved when compound(s) of theformula (I) is/are employed at levels of 250 to 500 ppb.

Interesting organoleptic effects, e.g. fat boosting effects, in edibleproducts containing fats can be achieved when compound(s) of the formula(I) is/are employed at levels of 500 to 1000 ppb.

It is particularly advantageous to incorporate compounds of formula (I)into edible products that are formed under conditions of hightemperature, such as baking, frying or which are processed by heattreatments such as pasteurization or under UHT conditions. Under highpreparation or processing temperatures, volatile flavour ingredients maybe lost or degraded with the result that flavour intensity can bereduced and the essential and authentic flavour characteristics can bediminished. Such edible products include dairy products, snack foods,baked products, powdered soft drinks and similar dry mixes, and thelike, fats and condiments, mayonnaise, dressings, soups and bouillons,and beverages.

Particularly preferred classes of edible product according to thepresent invention are powdered soft drinks and similar dry mixapplications. Dry mix applications are known in the art and includedproducts in powder form that are intended to be reconstituted beforeconsumption. They include powdered soups, powdered cake mixes, powderedchocolate drinks, instant coffees, seasonings and fonds, and the like.

Dry powders formed by dispersive evaporation processes, such as spraydrying, represent a very convenient vehicle to deliver flavour oilquality flavours to edible products.

Unfortunately, flavour oils, and in particular citrus flavour oils canbe particularly sensitive to dispersive evaporation processes,especially processes carried out at high temperature. Flavour oils tendto evaporate or degrade to form products having unfavourable off-notes.Powdered flavour compositions, particularly those containing citrusoils, can be of poor quality and exhibit relatively short self-life, asa result.

Surprisingly, the incorporation of compounds of formula (I) or flavourcompositions containing same into powder products, results in powderproducts that exhibit the impact and authenticity of the flavour oilsused in their preparation, essentially maintaining flavour oil qualityin a powdered flavour formulations.

Accordingly, the invention provides in another aspect a powder flavourproduct comprising a compound according to formula (I) and at least oneadditional flavour co-ingredient.

In another aspect of the invention there is provided a powder soft drinkproduct or other dry mix product comprising a compound according toformula (I).

In yet another aspect of the present invention there is provided apowdered soft drink product or other dry mix product comprising a powderflavour composition comprising a compound of formula (I).

In yet another aspect of the present invention there is provided amethod of forming a powder flavour product comprising the step ofincorporating into said composition a compound according to formula (I).

In a particular embodiment of the compound of formula (I) may be addedto the formed powder flavour product, or it may be added to flavourcomposition before forming the powder product.

Another particularly preferred class of edible product according to thepresent invention is snack food. Snack food is a category of productwell known to the skilled person in the food industry. These productsare described above and include, without limitation, pretzels, cornchips, potato chips, puffed products, extruded products, tortilla chipsand the like. Still more particularly, the invention is concerned withlow fat snack food compositions. Low fat snack food compositions containless that 30% by weight fat, more particularly between 5 to 25% byweight of fat.

A problem with reducing fat in a snack food product is the loss in tasteand texture. Fats play an important role in the way that dough behavesduring processing and greatly affect the quality, flavor and texture ofready-to-eat products. As the fat content in snack products is reducedor replaced with other ingredients (e.g., non-digestible fat, protein,fiber, gums), adverse organoleptic effects (e.g., mouth coating, drying,lack of crispness and lack of flavour) are increased. The adverseorganoleptic effects result in products having reduced palatability.

Considerable efforts have been expended in devising flavour compositionsto overcome the problems associated with low fat snack food products.Flavours may be applied to a snack food as topical coatings in the formof dry powders and/or as liquids (e.g., oil-based, water-based). Anotherapproach has been to add flavour to the dough.

Despite these various approaches which have been taken to improveconsumer appeal and palatability of snack foods, and particularly lowfat snack foods, there is still a need for improved low-fat snack foodshaving coatings applied thereto with the visual appeal, flavour, andtexture of full-fat snack foods.

Compounds according to formula (I) or flavour compositions containingsame can be incorporated into snack foods to impart an impactful flavourand a mouth feel with a remarkable roundness and fullness. Furthermore,the taste and mouth feel effects can be achieved even in low fat snackfoods.

Accordingly, the invention provides in another of its aspects a snackfood comprising a flavour composition as hereinabove described. In aparticular embodiment of the invention the snack food has a fat contentof about 40% or less by weight based on the total weight of the snackfood, more particularly about 30% or less, still more particularly 25%or less, more particularly still about 10% or less, still moreparticularly about 5% or less, still more particularly about 3% or less.

Examples of snack foods are described above and include productsprocessed by oven baking, extrusion or frying, and which are made frompotato and/or corn and/or various grains such as rice or wheat.

Another particularly preferred class of edible product according to thepresent invention is alcoholic beverages.

Applicant surprisingly found that compounds according to formula (I)incorporated into an alcoholic beverage had the effect of increasing thealcohol impact of the beverage.

Accordingly, the invention provides in another of its aspects analcoholic beverage comprising a compound according to formula (I).

In yet another aspect of the invention there is provided a method ofproducing a heightened alcoholic impression in an alcoholic beverage byincorporating into said beverage a compound according to formula (I).

Compounds of formula (I) may be incorporated into said alcoholicbeverage in amounts of 1 ppb to 1 ppm.

Other classes of edible product are products taken orally in the form oftablets, capsules, powders, multiparticulates and the like. Suchproducts may include pharmaceutical dosage forms or nutraceutical dosageforms.

Certain groups of people have problems swallowing tablets or capsules,powders, multi-particulates and the like. This problem can beparticularly pronounced in certain consumer groups, such as children andthe very old or infirm. Applicant surprisingly found that compoundsaccording to the formula (I) when taken into the oral cavity produce apronounced salivating effect. Incorporating the compounds into theseforms, particularly as part of a coating around said dosage forms canease the swallowing process for consumers, in particular children andthe old or infirm.

Accordingly, the invention provides in another of its aspects an orallyadministrable dosage form, in particular in the form of tabletscapsules, powders or multi-particulates comprising a compound accordingto the formula (I).

Another preferred class of edible product is baked goods. Compounds ofthe formula (I) may be incorporated topically or in-dough. Incorporatedat levels of 1 ppb to 1 ppm, the compounds of formula (I) render bakedproducts less dry and more succulent.

Other preferred class of edible products are caloric or non-caloricbeverages containing carbohydrate sweeteners, such as sucrose, highfructose corn syrup, fructose and glucose, or high intensity,non-nutritive sweeteners such as aspartame, acesulfame K, sucralose,cyclamate, sodium saccharin, neotame, rebaudioside A, and/or otherstevia-based sweeteners; as well as other optional ingredients such asjuices, organic acids such as citric acid, alcohol and functionalingredients.

Incorporated at levels of 1 ppb to 10 ppm, compounds of formula (I)impart to said beverages containing sweeteners at levels of less than 1%and up to about 20%, an up-front sweetness and mouthfeel that isreminiscent of sugar.

Other preferred edible products are savoury products, in particularthose that are soy-based or fish-based.

Incorporated at levels of 1 ppb to 10 ppm, in a soy-based products (suchas soy sauce) or a fish-based product (such as fish sauce) containing 5to 40% salt, the products are found to exhibit strong umami tastes thatare long-lasting and rich.

Another preferred edible product is a clouded beverage product.

Certain beverages such as juices have relatively higher turbidity andthus have an opaque appearance. Often, it is desired that the beveragehave a relatively high turbidity. This might be desirable to provide amore natural appearance to beverages with low juice content, or it mightbe for reasons related to masking sedimentation or “ringing” (whereflavour or colour oils rise to the surface of a container duringstorage). Clouded beverages are usually formed by means of a cloudingagent. Clouding agents are usually supplied in the form of emulsions, orthe clouding agent may be part of a powdered beverage that uponreconstitution will formed an emulsion providing a permanent cloud tothe beverage.

Compounds of the formula (I), in addition to their organolepticproperties, can lend stability to clouding agents and to beveragecompositions containing same.

Accordingly, the invention provides in another of its aspects acomposition comprising a beverage clouding composition and a compound offormula (I).

In a particular embodiment of the invention, a flavour composition asherein defined may be provided in the form of an emulsion. This emulsioncomposition may be particularly useful in clouded beverage applications,in particular, in which it is intended to employ a clouding agent.

In yet another aspect of the invention there is provided a cloudedbeverage composition comprising a clouding agent and a compound of theformula (I).

Other preferred edible products are those that are formed by a processof ripening.

In food processing, it frequently occurs that a food needs to remain fora prolonged period of time and under well-defined conditions to obtainthe food with the requisite and recognised quality. A commonly used termfor this process is ripening. Ripening is well known in the processingof certain types of cheese, meat, soy-sauce and wine, as well as beersausage, sauerkraut, tempeh and tofu. There are also specific steps thatare carried out for specific reasons (such as water-removal, or off-noteremoval) that have beneficial effects on the food products. Examples ofthis are the conching of chocolate and the drying of noodles, vegetablesand fruits. The transformations that improve the quality of the food areinduced by chemical conversions, enzymatically catalysed conversions orfermentative transformations. All of these conversions are slow andtherefore expensive; they are also not fully predictable orcontrollable.

The compounds of formula (I), having regard to the property of adding tothe authentic taste characteristics of the edible products in which theyare incorporated, may be added to an edible product during its ripeningprocess in order to reduce storage time without adversely influencingthe taste quality of the ripened product.

Accordingly, in another aspect of the invention there is provided amethod of ripening a product selected from the group consisting ofcheese, meat, soy-sauce and wine, beer, sausage, sauerkraut, tempeh andtofu, comprising the step of ripening the product in the presence of acompound according to the formula (I).

In another aspect of the invention there is provided a method ofconching chocolate, said method comprising the step of adding to thechocolate a compound according to the formula (I), or a flavourcomposition containing same.

There now follows a series of non-limiting examples that serve toillustrate the invention.

EXAMPLE 1 Preparation Linoleoyl Chloride

1026 grams (3.659 moles (assuming 100% purity), 1.0 equiv.) of linoleicacid (mixture of fatty acids, approximately 60% pure based on linoleicacid moiety) and 8210 grams of THF (0.13% water) were mixed together ina reaction vessel. While stirring and cooling (cooling water temperature18.6° C.) 948 grams (7.32 moles, 2.0 equivalents) of oxalyl dichloride98% (Sigma Aldrich) was dosed in 50 minutes. Thereafter, stirring wascontinued for 120 minutes at room temperature (22° C.).

The reaction crude was concentrated in two steps. First distillation at180 mbar \ 40° C. was carried out to obtain 5594 grams of distillate.This was removed and transferred to a rotary evaporator. Concentratingwas continued till 55° C. and 30 mbar (reached in steps). The distillate(518 grams) was added to the earlier obtained solvent and excess oxalyldichloride. The clear dark brown concentrate (1170 grams) will be usedin the next step.

Preparation 4-((9Z,12Z)-octadeca-9,12-dienamido)butanoic acid(C18:2-GABA or GABA linoleic acid compound) solution in propylene glycol

A reaction vessel was charged with a mixture of 7016 grams of water and280.7 grams (7.02 moles) of sodium hydroxide pellets. To the mixture wasadded 401.5 grams (3.89 moles, 1.247 equiv.) of gamma amino butyric acid(GABA) and 6244.6 grams of THF. While stirring the contents were cooledto 10° C. Over a period of 1 hour, 935.5 grams (3.13 moles (based on100% purity, 1.0 equiv.) of linoleoyl chloride prepared in accordancewith the aforementioned method added to the mixture. During the dosagethe temperature range was 10° C.-6.5° C. While cooling stirring wascontinued for 1 hour, the temperature was 6.5° C. Cooling was stoppedand stirring was continued for an additional hour, the temperature roseto 8.0° C.

The crude product was acidified by dosing 579 grams (5.79 moles) ofhydrochloric acid 36%. The pH was adapted from 12.17 to 2.0. After theaddition of the acid, stirring was stopped and the mixture was allowedto separate.

After the separation the light yellow lower aqueous phase was removed.The brown organic top phase was stored. The lower aqueous phase wasextracted with 3898 grams of ethyl acetate. After stirring andseparating the lower phase (8881 grams) was removed and stored. Theethyl acetate top phase (6375 grams) was added to the earlier obtainedorganic phase.

The combined mixture was washed with a brine solution made out of 585grams of sodium chloride and 5262 grams of water. After stirring andseparating, the lower brine phase (6800 grams) was removed and the brownorganic top phase was concentrated in two steps. Step 1 was concentratedat 40° C. and 170 mbar, whereas in step 2a rotary evaporator wasemployed to remove more solvent (and water) at 55° C. and 32 mbar. Intotal (steps 1 and 2) 6860 grams of distillate were obtained.1,2-propylene glycol (PG) was added.

To the product \ PG mixture 3235 grams of heptane and 312 grams of waterwas added. The entire mixture was added to a 10 liter separatory funnel.After shaking and separating, two phases were visible. The lower PG \product phase (4385 grams) was removed and the top heptane phase (2115grams) was stored.

Residual solvents in the product/propylene glycol (PG) phase wereremoved in a rotaty evaporator at 55° C. and 22 mbar (reached in steps).As the solvents and water were removed the PG \ product mixture becameclear. In the end 762 grams of distillate were obtained.

EXAMPLE 2

A spray dried powder of the GABA-Linoleic compound produced in Example 1was prepared in the following manner:

400 grams of maltodextrin (DE12) was added to 600 grams of water and26.7 grams of a propylene glycol solution (representing 1% of theGABA-linoleic acid compound after drying) to form a mixture. The mixturewas stirred vigorously at 20 degrees centigrade in an equal volume ofwater to form a feed. The feed is homogenized using an Ultra Turrax T25at 25,000 rpm for about 2 minutes. The homogenised feed is spray-driedin a NIRO MOBIL MINOR SPRAY DRYER using a rotary wheel atomiser at20,000 rpm. Inlet air temperature is kept at 190° C., resulting in anoutlet temperature in the range of 90° C.

A dried powder containing 1% GABA-linoleic acid compound was obtained.

The powder was equilibrated in a dessicator above a saturated saltsolution for 2 weeks under conditions of 50% relative humidity.Thereafter, the Tg of the equilibrated powder was measured by DSC(Perkin Elmer Pyrus Diamond DSC) using a closed cup method, as follows:A stainless steel cup is filled with the equilibrated powder and closedsuch that no water can evaporate during measurement. DSC measurement isundertaken using the heat-cool-heat measurement wherein heating iscarried out at 10° C./min; cooling at 40° C./min; and heating again at10° C./min. The Tg measurement is calculate from the mid-point of acurve produced when heat flow is plotted against temperature on thesecond heat cycle.

1. A method of isolating and recovering a compound according to theformula (I)

wherein R₁ together with the carbonyl group to which it is attached is aresidue of a carboxylic acid, and NR₂R₃, in which R₃ is H or togetherwith R₂ and the N-atom to which they are attached, a 5-membered ring, isa residue of an amino acid, and is preferably a proteinogenic aminoacid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-aminocycloalkyl carboxylic acid; from a reaction mixture comprising thecompound in a reaction solvent, the method comprising the steps of:prior to removal of reaction solvent from the reaction mixture byevaporation, adding to the reaction mixture an extraction solvent forthe compound, said extraction solvent having a higher boiling point thanthe reaction solvent, and subsequent to the evaporation of and removalof the reaction solvent from the reaction mixture containing thecompound of formula (I), the reaction solvent and the extractionsolvent, the compound of formula (I) is recovered in the form of a stocksolution containing the compound of formula (I) in the extractionsolvent.
 2. A method of forming a stock solution comprising the stepsof: isolating and recovering a compound according to the formula (I)

wherein R₁ together with the carbonyl group to which it is attached is aresidue of a carboxylic acid, and NR₂R₃, in which R₃ is H or togetherwith R₂ and the N-atom to which they are attached, a 5-membered ring, isa residue of an amino acid, and is preferably a proteinogenic aminoacid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-aminocycloalkyl carboxylic acid; from a reaction mixture comprising thecompound in a reaction solvent, the method comprising the steps of:prior to removal of the reaction solvent from the reaction mixture byevaporation, adding to the reaction mixture an extraction solvent forthe compound which has a higher boiling point than the boiling point ofthe reaction solvent, and, subsequently, separating the compoundaccording to formula (I) from the reaction solvent, and recovering fromthe reaction mixture a stock solution containing the compound and theextraction solvent.
 3. A method according to claim 1 wherein theextraction solvent is selected from water-miscible alcohols andderivatives thereof.
 4. A method according to claim 3 wherein theextraction solvent is selected from: ethanol, glycerol, propyleneglycol, triacetine or miglyol, or mixtures thereof.
 5. A methodaccording to claim 3, wherein the extraction solvent is propyleneglycol.
 6. A stock solution comprising up to 25% by weight of a compoundof formula (I)

wherein R₁ together with the carbonyl group to which it is attached is aresidue of a carboxylic acid, and NR₂R₃, in which R₃ is H or togetherwith R₂ and the N-atom to which they are attached, a 5-membered ring, isa residue of an amino acid, and is preferably a proteinogenic aminoacid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-aminocycloalkyl carboxylic acid; in a solvent selected from water-misciblealcohols and/or derivatives thereof.
 7. A stock solution according toclaim 6 wherein the solvent is selected from: ethanol, glycerol,ethylene glycol, propylene glycol, triacetine or miglyol, or mixturesthereof.
 8. A stock solution according to claim 6, wherein the solventis propylene glycol.
 9. A stock solution according to claim 6 whereinthe compound of formula (I) is present in an amount of up to 15% byweight.
 10. A spray dried powder comprising a compound according toformula (I)

wherein R₁ together with the carbonyl group to which it is attached is aresidue of a carboxylic acid, and NR₂R₃, in which R₃ is H or togetherwith R₂ and the N-atom to which they are attached, a 5-membered ring, isa residue of an amino acid, and is preferably a proteinogenic aminoacid, ornithine, gamma-aminobutyric acid or beta alanine, or a 1-aminocycloalkyl carboxylic acid.
 11. A spray dried powder according to claim10, comprising a carrier material selected from a maltodextrin having adextrose equivalent (DE) of 3 to 25, or gum Arabic.
 12. A spray driedpowder according to claim 10 wherein the compound of formula (I) ispresent in an amount of up to 1.5% by weight based on the total weightof the powder.
 13. A spray dried powder according to claim 10 formedfrom a stock solution according to claim 6.